Deodorization of peracids

ABSTRACT

The present invention relates to compositions of peracids, such as peroxycarboxylic acids, having reduced odor compared to conventional peracid compositions. The invention further relates to methods employing such compositions, and methods of making these compositions. Typically, the reduced-odor antimicrobial compositions include an alcohol for the esterification reaction to remove short- to mid-chain length malodorous carboxylic acids.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation application of U.S. Ser. No. 13/542,735 filedJul. 6, 2012, which application claims priority to U.S. ProvisionalApplication Ser. No. 61/507,678 filed on Jul. 14, 2011 and entitledDeodorization of Peracids. The entire contents of these patentapplications are hereby expressly incorporated herein by referenceincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof.

This application is also related to U.S. application Ser. No. 13/542,742(Ecolab Case No. 2941USU2) filed Jul. 6, 2012 and entitled EnhancedAntimicrobial Peracid Compositions and Methods of Use at ReducedTemperatures in Aseptic Cleaning. The entire contents of this patentapplication are also expressly incorporated herein by referenceincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof.

FIELD OF THE INVENTION

The invention relates to compositions of peracids, such asperoxycarboxylic acids, having reduced odor compared to conventionalperacid compositions. In aspects of the invention, the reduced odorperacids demonstrate at least substantially similar antimicrobialefficacy as peracid compositions not employing the esters generatedaccording to the compositions and methods of the invention. The presentinvention further relates to methods employing these reduced-odorperacid compositions, and methods of making the same. In a particularaspect of the invention, the reduced-odor peracid compositions includean alcohol for the esterification reaction to remove short chainmalodorous carboxylic acids and generate compositions having a lower useconcentration.

BACKGROUND OF THE INVENTION

Peracid compositions, namely peroxycarboxylic acid compositions, exhibituseful antimicrobial and bleaching activity. Conventionalperoxycarboxylic acid compositions typically include short chainperoxycarboxylic acids or mixtures of short chain peroxycarboxylic acidsand medium chain peroxycarboxylic acids (see, e.g., U.S. Pat. Nos.5,200,189, 5,314,687, 5,409,713, 5,437,868, 5,489,434, 6,674,538,6,010,729, 6,111,963, and 6,514,556, each incorporated by reference inits entirety).

A majority of existing peracid compositions, including peroxycarboxylicacids, suffer from unacceptable odors which are an inherent disadvantageof the compositions and limit their use in cleaning applications. Oftenthe peracid compositions exhibit a sharp, annoying, or otherwiseunacceptable odor that increases as the composition ages, beginningwithin as soon as a few weeks of formulation. Such malodorssignificantly limit the applications suitable for using suchperoxycarboxylic acid compositions. It would be undesirable to applysuch peroxycarboxylic acid compositions to large surfaces areas (e.g.floor cleaners).

According to the invention, there is a need for low or no odorantimicrobial peroxycarboxylic acid compositions.

It is an objective of the claimed invention to develop a peracidchemistry composition having a lower odor profile at the same or loweruse temperatures.

A further object of the invention is a peracid composition eliminatingthe shorter carboxylic acids chains responsible for malodors of peracidchemistries.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to peracid compositions having reducedodor compared to conventional peracid compositions and/or peracidcompositions that do not have ester components, methods employing thesereduced-odor peracid compositions, and methods of making the same.Typically, the compositions according to the present invention includean alcohol for esterification and removal of short chain malodorouscarboxylic acids.

In an aspect of the invention, a reduced odor peroxycarboxylic acidcomposition is provided. The composition comprises from about 0.01 wt-%to 50 wt-% of at least one peroxycarboxylic acid; and from about 0.1wt-% to 20 wt-% of an alcohol, wherein the the alcohol is effective forforming alkyl esters under the same conditions for peroxycarboxylic acidformation to reduce the malodors of the peroxycarboxylic acidcompositions associated with short to mid-chain length carboxylic acidscontaminants and/or those formed due to degradation of aperoxycarboxylic acid composition.

In a further aspect of the invention, a method for generating reducedodor antimicrobial peroxycarboxylic acid compositions is provided. Themethod includes providing an alcohol to a peroxycarboxylicacid-generating composition, wherein the alcohol is provided before orduring formation of peroxycarboxylic acids to generate alkyl esters thatare capable of removing and/or masking short chain carboxylic acidsassociated with malodors; and generating an peroxycarboxylic acidcomposition that is stable for at least 1 year at room temperaturewithout the development of malodors and comprises from about 0.01 wt-%to 50 wt-% of at least one peroxycarboxylic acid selected from the groupconsisting of an alkyl peroxycarboxylic acid, a sulfoperoxycarboxylicacid and combinations of the same; and about 0.1 wt-% to 20 wt-% of analcohol selected from the group consisting of methanol, ethanol,propanol, butanol, nonanol, benzyl alcohol and combinations of the same,wherein the alcohol is effective for forming ethyl esters in theperoxycarboxylic acid composition.

In a still further aspect of the invention, a method of reducingpopulation of microorganism on an object is provided and comprisescontacting an object a the reduced-odor peroxycarboxylic acid comprisingat least one peroxycarboxylic acid and an alcohol, wherein the alcoholis effective for forming alkyl esters under the same conditions forperoxycarboxylic acid formation to reduce the odor of theperoxycarboxylic acid and the composition comprises from about 0.01 wt-%to 50 wt-% peroxycarboxylic acid and from about 0.1 wt-% to 20 wt-%alcohol.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to antimicrobial compositions including aneffective antimicrobial amount of a peracid and an alcohol. Thecomposition of the invention has reduced odor of peracid compared to acomposition lacking the alcohol. In an aspect, the reduced-odorantimicrobial composition can be used at a lower use concentration whileeffectively reducing microbial populations, including difficult to killendospore forming bacilli type bacteria which are not killed bycommodity peracid compositions. The compositions can be used on avariety of hard surfaces such as those in facilities and equipment usedin the food and beverage industries. Additionally, the presentcomposition can be used to effectively reduce the microbial populationof food, of dishware, and to treat water.

The embodiments of this invention are not limited to particularcompositions, methods of use and methods of making, which can vary andare understood by skilled artisans. It is further to be understood thatall terminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting in any manner orscope. For example, as used in this specification and the appendedclaims, the singular forms “a,” “an” and “the” can include pluralreferents unless the content clearly indicates otherwise. Further, allunits, prefixes, and symbols may be denoted in its SI accepted form.Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities refers to variation inthe numerical quantity that can occur.

The term “alkyl” or “alkyl groups,” as used herein, refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups). Unless otherwisespecified, the term “alkyl” includes both “unsubstituted alkyls” and“substituted alkyls.” As used herein, the term “substituted alkyls”refers to alkyl groups having substituents replacing one or morehydrogens on one or more carbons of the hydrocarbon backbone. Suchsubstituents may include, for example, alkenyl, alkynyl, halogeno,hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy,aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano,amino (including alkyl amino, dialkylamino, arylamino, diarylamino, andalkylarylamino), acylamino (including alkylcarbonylamino,arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio,arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonates,sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed bacteriocidal and thelater, bacteriostatic. A sanitizer and a disinfectant are, bydefinition, agents which provide antibacterial or bacteriocidalactivity. In contrast, a preservative is generally described as aninhibitor or bacteriostatic composition.

For the purpose of this patent application, successful reduction ofmicroorganisms is achieved when the populations of microorganisms arereduced by about 50%, by significantly more than is achieved by a washwith water, or at least about 0.3-1 log₁₀. Larger reductions inmicrobial population provide greater levels of protection. In thisapplication, such a population reduction is the minimum acceptable forthe processes. Any increased reduction in population of microorganismsis an added benefit that provides higher levels of protection.

The term “disinfectant,” as used herein, refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

The phrase “food processing surface” or “food surface,” as used herein,refers to a surface of a tool, a machine, equipment, a structure, abuilding, or the like that is employed as part of a food processing,preparation, or storage activity. Examples of food processing surfacesinclude surfaces of food processing or preparation equipment (e.g.,slicing, canning, or transport equipment, including flumes), of foodprocessing wares (e.g., utensils, dishware, wash ware, and bar glasses),and of floors, walls, or fixtures of structures in which food processingoccurs. Food processing surfaces are found and employed in foodanti-spoilage air circulation systems, aseptic packaging sanitizing,food refrigeration and cooler cleaners and sanitizers, ware washingsanitizing, blancher cleaning and sanitizing, food packaging materials,cutting board additives, third-sink sanitizing, beverage chillers andwarmers, meat chilling or scalding waters, sanitizing gels, coolingtowers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

The phrase “health care surface,” as used herein, refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.), or woven andnon-woven surfaces (such as surgical garments, draperies, bed linens,bandages, etc.), or patient-care equipment (such as respirators,diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.), orsurgical and diagnostic equipment. Health care surfaces include articlesand surfaces employed in animal health care.

The term “heterocyclic group,” as used herein (e.g. referring tosubstituted alkyls including a heterocyclic group), includes closed ringstructures analogous to carbocyclic groups in which one or more of thecarbon atoms in the ring is an element other than carbon, for example,nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated orunsaturated. Exemplary heterocyclic groups include, but are not limitedto, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan.

The term “instrument,” as used herein, refers to the various medical ordental instruments or devices that can benefit from cleaning with areduced-odor composition according to the present invention. The phrases“medical instrument”, “dental instrument”, “medical device”, “dentaldevice”, “medical equipment”, or “dental equipment” refer toinstruments, devices, tools, appliances, apparatus, and equipment usedin medicine or dentistry. Such instruments, devices, and equipment canbe cold sterilized, soaked or washed and then heat sterilized, orotherwise benefit from cleaning in a composition of the presentinvention. These various instruments, devices and equipment include, butare not limited to: diagnostic instruments, trays, pans, holders, racks,forceps, scissors, shears, saws (e.g. bone saws and their blades),hemostats, knives, chisels, rongeurs, files, nippers, drills, drillbits, rasps, burrs, spreaders, breakers, elevators, clamps, needleholders, carriers, clips, hooks, gouges, curettes, retractors,straightener, punches, extractors, scoops, keratomes, spatulas,expressors, trocars, dilators, cages, glassware, tubing, catheters,cannulas, plugs, stents, arthoscopes and related equipment, and thelike, or combinations thereof.

The terms “agricultural” or “veterinary” objects or surfaces, as usedherein, include animal feeds, animal watering stations and enclosures,animal quarters, animal veterinarian clinics (e.g. surgical or treatmentareas), animal surgical areas, and the like.

The term “microorganisms,” as used herein, refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),lichens, microfungi, protozoa, virinos, viroids, viruses, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

The terms “mixed” or “mixture” when used relating to “peracidcomposition,” “peroxycarboxylic acid composition,” “peracids” or“peroxycarboxylic acids” refer to a composition or mixture includingmore than one peracid, such as a peroxycarboxylic acid, such as acomposition or mixture including peroxyacetic acid and peroxyoctanoicacid.

The phrases “objectionable odor,” “offensive odor,” or “malodor,” asused herein, refer to a sharp, pungent, or acrid odor or atmosphericenvironment from which a typical person withdraws if they are able to.Hedonic tone provides a measure of the degree to which an odor ispleasant or unpleasant. An “objectionable odor,” “offensive odor,” or“malodor” has an hedonic tone rating it as unpleasant as or moreunpleasant than a solution of 5 wt-% acetic acid, propionic acid,butyric acid, or mixtures thereof.

The term “object”, as used herein, refers to a something material thatcan be perceived by the senses, directly and/or indirectly. Objectsinclude a surface, including a hard surface (such as glass, ceramics,metal, natural and synthetic rock, wood, and polymeric), an elastomer orplastic, woven and non-woven substrates, a food processing surface, ahealth care surface, and the like. Objects also include a food product(and its surfaces); a body or stream of water or a gas (e.g., an airstream); and surfaces and articles employed in hospitality andindustrial sectors.

The term “sanitizer,” as used herein, refers to an agent that reducesthe number of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25° C.+/−2° C., against several test organisms.

The phrase “short chain carboxylic acid,” as used herein, refers to acarboxylic acid that has characteristic bad, pungent, or acrid odor.Examples of short chain carboxylic acids include formic acid, aceticacid, propionic acid, and butyric acid.

The term “sporicide,” as used herein, refers to a physical or chemicalagent or process having the ability to cause greater than a 90%reduction (1-log order reduction) in the population of spores, such asspores of Bacillus cereus or Bacillus subtilis, within 30 minutes atambient temperature. In certain embodiments, the sporicidal compositionsof the invention provide greater than a 99% reduction (2-log orderreduction), greater than a 99.99% reduction (4-log order reduction), orgreater than a 99.999% reduction (5-log order reduction) in suchpopulation within at least 30 minutes at ambient temperature.

The term “substantially similar” when referring to the cleaningperformance and/or antimicrobial efficacy of compositions according tothe invention is a comparison to conventional compositions and thecleaning performance and/or antimicrobial efficacy obtained from thesame. In an aspect of the invention, there is generally the same degree(or at least not a significantly lesser degree) of cleanliness (i.e.cleaning and/or antimicrobial efficacy) or with generally the sameexpenditure (or at least not a significantly lesser expenditure) ofeffort, or both between the compositions according to the invention andthose conventional compositions that do not employ an alcohol for theesterification reaction to remove short- to mid-chain length malodorouscarboxylic acids.

The term “ware,” as used herein, refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polycarbonate polymers (PC), acrilonitrile-butadiene-styrenepolymers (ABS), and polysulfone polymers (PS). Another exemplary plasticthat can be cleaned using the compounds and compositions of theinvention include polyethylene terephthalate (PET).

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the component and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods, systems, apparatuses, and compositions.

Peracid Compositions

While an understanding of the mechanism is not necessary to practice thepresent invention and while the present invention is not limited to anyparticular mechanism of action, it is contemplated that, in someembodiments, the peroxycarboxylic acid compositions using an alcohol,such as ethanol, can remove and/or mask short to mid-chain malodorsinherent in traditional peracids. As one skilled in the art appreciates,peracid compositions change with age. For example, in approximately oneyear at ambient conditions the amount of peroxycarboxylic acid in acompositions can decrease to about 50% to about 80% or greater, of theinitial equilibrium values or use composition levels. Long chainperacids, such as carbon lengths of about C18 or greater, can slowlydegrade from the odorless initial structures to the malodorous C8 andshorter carboxylic acids. The shorter carboxylic acids are more volatileand ultimately appear responsible for the malodors for which the presentinvention seeks to improve. In contrast, the larger molecular weightcarboxylic acid molecules have low odors in part due to the variousintermolecular bonding functional groups and vapor pressures being solow that little to no odor is detectable.

According to an embodiment of the invention, though not intending to belimited to a particular theory of the embodiment, use of an alcohol,such as ethanol, in the peroxycarboxylic acid compositions of thepresent invention, forms ethyl esters under these same conditions thatfavor peracid formation. As one of skill in the art will ascertain fromthe description of the present invention, although there is significantliterature describing the formation of percarboxylic acids throughoxidation processes, the percarboxylic acid formation can also bedescribed as an esterification process. In an esterification process theperoxycarboxylic acid can be considered essentially an ester. Forexample, the formation of peroxycarboxylic acids is usually representedby the following equilibrium process:

RCO₂H+R′OH

RCO₂R′+H₂O

When R′ is a hydroxyl group, peroxycarboxylic acids are generated.However, when R′ is an alkyl group, such as CH₃CH₂, the ethyl ester ofthe same parent carboxylic acid is generated. In the equilibrium processanything removed from the product side will cause the system to produceadditional product, such that the removal or minimization of waterfavors the production of the RCO₂R′ species.

According to the present invention, employing conditions that favorperacid formation, such as dehydration of the system by the addition ofsulfuric acid or LAS/DDBSA or minimizing water, will similarly alsofavor esterification. In an embodiment, the addition of ethyl alcohol toa peracid-forming mixture (also referred to herein as a peroxycarboxylicacid-generating composition) results in the formation of the ethyl esteranalogs of the peroxycarboxylic acids.

In an exemplary embodiment, a concentrated hard surface disinfectantcontaining an antimicrobial anionic surfactant (e.g. dodecyl benzenesulfonic acid (DDBSA)) for use at high dilution rates is generatedaccording to the invention. For example, a concentrated DDBSA (i.e.concentrations approximating 30%) and sulfuric acid (i.e. about 3%),such as set forth in Example 1, combine as very strong dehydratingagents to remove water from the product side of the peracid equilibrium.These conditions strongly favor the formation of peroxycarboxylic acids.However, such strongly dehydrating conditions while benefiting theefficient conversion of carboxylic acids to the peroxycarboxylic acids,this similarly results in accelerating C-chain degradation of thepercarboxylic acid (PSOA), as evidenced by the increase in medium-chainfatty acid odors. As a result, an initially odorless long chain peracid(e.g. PSOA chemistry) generates objectionable malodors prior to use,especially when used on large surface areas (e.g. floors, etc.).Beneficially, as provided according to the present invention, theaddition of a small amount of alcohol, within minutes to hours, resultsin the prevention of these malodors. In an embodiment, the malodors areonly minimally apparent due to the conversion of some or most of thefree short chain carboxylic acids to the respective ester.

In an embodiment of the invention, the addition of a short chainalcohol, such as ethyl alcohol, results in a pleasant odor such as afruity odor. In some aspects, the use of a short chain alcohol resultsin an odor similar to ethyl caprylate. Beneficially, the production of apleasant odor requires only small quantity of an alcohol. In certainembodiments, alcohol quantities of less than about 10 wt-%, andpreferably less than about 5 wt-% are employed according to certainembodiments of the invention.

In an aspect of the invention, the reduction of malodors is achieved. Inone embodiment, short chain alcohols (e.g. ethyl alcohol) are employedto generate esters in a peracid composition. In a further aspect of theinvention, an alcohol having a longer carbon chain and/or lower vaporpressure may be employed, as is further demonstrated in Example 3 (Table5).

In an aspect of the invention, the compositions and methods provide morethan a mere mask for malodors associated with peroxycarboxylic acids.This is demonstrated by the minor loss in peroxycarboxylic acids whenemploying the methods of the present invention. Surprisingly, theaddition of a short chain alcohol in small amounts (e.g. less than about5 wt-% ethyl alcohol) does not cause significant losses inperoxycarboxylic acid, as demonstrated in Example 1 (Table 4).Preferably, there is less than about 5% loss of peroxycarboxylic acidaccording to the invention, preferably less than about 2% loss, morepreferably less than about 1% loss.

In a further aspect of the invention, a malodor derivitization processis provided, wherein the malodor derivitization process provides anadditional benefit of generating a pleasant odor.

In a further benefit of the invention, the formation of the ethylesters, which are water soluble to slightly water soluble esters, mayunexpectedly result in enhanced micro efficacy of the peroxycarboxylicacids. In an alternative aspect of the invention, the ethyl esters donot detrimentally impact the antimicrobial efficacy of the peracidcompositions according to the invention. Preferably, the ethyl estersemployed in the reduced-odor peracid compositions according to theinvention provide at least substantially-similar cleaning and/orantimicrobial efficacy as peracid compositions that do not employalcohols to form such ethyl esters.

The present invention relates to reduced-odor peracid compositionscontaining a peroxycarboxylic acid and an alcohol. Preferably, thereduced-odor peracid compositions further include an acidic anionicsurfactant. The peroxycarboxylic acid and the acidic anionic surfactantare antimicrobial agents. Surprisingly, the peroxycarboxylic acid (orthe peroxycarboxylic acid and acidic anionic surfactant) compositionsaccording to the invention do not exhibit the unacceptable odor when analcohol is added to the formulation. According to an embodiment, use ofan alcohol, such as ethanol, reduces or eliminates the malodor of theperoxycarboxylic acid (or combination of the peroxycarboxylic acid andacidic anionic surfactant) compared to a composition lacking thealcohol.

The peroxycarboxylic acid composition according to the invention is madein the presence of the alcohol, rather than using an alcohol adjuvantthat is added after forming the peroxycarboxylic acid. The alcohol istypically present in the peroxycarboxylic acid composition in a quantitythat effectively reduces odor of the peroxycarboxylic acid.

Suitable levels of an alcohol in a concentrate composition according tothe invention include a mole ratio of alcohol to peroxycarboxylic acidof at least from about 160:1 alcohol to peracid to about 1:10 for aconcentrate composition according to the invention. In a preferredembodiment, the mole ratio of alcohol to peroxycarboxylic acid for aconcentrate composition is from about 120:1 to about 1:20, or from about100:1 to about 1:25. It is to be understood that all ranges and valuesbetween these ranges and values are encompassed by the presentinvention.

In an embodiment of the invention, a concentrate composition includesabout 0.01 to 50 wt-% peroxycarboxylic acid and from about 0.1 to 20wt-% alcohol. In a further embodiment, the composition includes about 1to about 50 wt-% peroxycarboxylic acid and from about 1 to 10 wt-%alcohol. In a still further embodiment, the composition includes about10 to about 50 wt-% peroxycarboxylic acid and from about 1 to 5 wt-%alcohol. It is to be understood that all ranges and values between theseranges and values are encompassed by the present invention.

Suitable levels of an alcohol in a ready to use (RTU) compositionaccording to the invention include a mole ratio of alcohol toperoxycarboxylic acid of at least from about 500:1 to about 3:1. In apreferred embodiment, the mole ratio of alcohol to peroxycarboxylic acidfor a RTU composition is from about 500:1 to about 10:1, or from about1400:1 to about 20:1. It is to be understood that all ranges and valuesbetween these ranges and values are encompassed by the presentinvention.

In an embodiment of the invention, a RTU composition includes about 0.01to 10 wt-% peroxycarboxylic acid and from about 0.01 to 10 wt-% alcohol,preferably from about 0.04 to 50 wt-% peroxycarboxylic acid and fromabout 0.1 to 5 wt-% alcohol. It is to be understood that all ranges andvalues between these ranges and values are encompassed by the presentinvention.

Each of the compositions can be formulated by combining each of thelisted ingredients. The peroxycarboxylic acid compositions areformulated to provide an equilibrium composition, wherein the peracidexists in equilibrium with its corresponding carboxylic acid andhydrogen peroxide (or other oxidizing agent). According to the inventionthe peroxycarboxylic acid compositions reach an equilibrium afterapproximately one week at room temperature.

Typically, the pH of an equilibrium mixture is less than about 1 orabout 2, and the pH of a 1% solution of the equilibrium mixture in wateris about 2 to about 9, depending on the other components of the 1%solution, and the pH of a use composition can be from about 1 to about 9depending on the other components. Preferably, compositions according tothe invention have a pH less than about 7, or from about 1 to 7. It isto be understood that all ranges and values between these ranges andvalues are encompassed by the present invention.

The peroxycarboxylic acid compositions of the present invention havesubstantially no odor or low odor. As referred to herein, low odor mayinclude the slightly sweet smell of the ethyl esters produced in theperoxycarboxylic acid compositions as a result of the inclusion ofalcohol in the compositions. Such low odor would be easily recognized asa pleasant odor, as opposed to the distinct malodors commonly associatedwith peroxycarboxylic acid compositions that do not include the alcoholsas set forth in the present invention.

The peroxycarboxylic acid compositions of the present invention have atleast the same stability as conventional, commercially-availableperoxygen containing compositions. In some embodiments, the compositionsof the present invention are stable for at least about 2 years at roomtemperature. In further embodiments, the compositions of the presentinvention are stable for at least about 1 year at room temperature.

Peroxycarboxylic Acids

A variety of peroxycarboxylic acids may be employed in the compositionsaccording to the invention. According to an embodiment of the inventionsuitable peroxycarboxylic acids include ester peroxycarboxylic acids,alkyl ester peroxycarboxylic acids, sulfoperoxycarboxylic acids, andcombinations of several different peroxycarboxylic acids, as describedherein. According to an additional embodiment of the invention one ormore carboxylic acids may also be used in the compositions disclosedherein.

Peroxycarboxylic (or percarboxylic acid or peracids) refer synonymouslyto acids having the general formula R(CO₃H)_(n). The R group can besaturated or unsaturated as well as substituted or unsubstituted. Asdescribed herein, R is an alkyl, arylalkyl, cycloalkyl, aromatic,heterocyclic, or ester group, such as an alkyl ester group. N is one,two, or three, and named by prefixing the parent acid with peroxy. Estergroups are defined as R groups including organic moieties (such as thoselisted above for R) and ester moieties. Exemplary ester groups includealiphatic ester groups, such as R₁OC(O)R₂, where each of R₁ and R₂ canbe aliphatic, preferably alkyl, groups described above for R. PreferablyR₁ and R₂ are each independently small alkyl groups, such as alkylgroups with 1 to 5 carbon atoms.

As one skilled in the art shall appreciate, peroxycarboxylic acids arenot as stable as carboxylic acids, their stability generally increaseswith increasing molecular weight. Thermal decomposition of these acidscan generally proceed by free radical and nonradical paths, byphotodecomposition or radical-induced decomposition, or by the action ofmetal ions or complexes. Percarboxylic acids can be made by the direct,acid catalyzed equilibrium action of hydrogen peroxide with thecarboxylic acid, by autoxidation of aldehydes, or from acid chlorides,and hydrides, or carboxylic anhydrides with hydrogen or sodium peroxide.

In some embodiments of the invention at least one peroxycarboxylic acidis employed. Exemplary peroxycarboxylic acids useful in the compositionsof the present invention include peroxyformic, peroxyacetic,peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic,peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic,peroxyundecanoic, peroxydodecanoic, peroxylactic, peroxycitric,peroxymaleic, peroxyascorbic, peroxyhydroxyacetic (peroxyglycolic),peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric,peroxyadipic, peroxypimelic, peroxysuberic, and peroxysebacic acid, andmixtures thereof. Useful peroxycarboxylic acids also include the esterperoxycarboxylic acids described herein and compositions of the presentinvention including those ester peroxycarboxylic acids. Peroxy forms ofcarboxylic acids with more than one carboxylate moiety can have one ormore of the carboxyl moieties present as peroxycarboxyl moieties. Theseperoxycarboxylic acids have been found to provide good antimicrobialaction with good stability in aqueous mixtures. In a preferredembodiment, the composition of the invention utilizes a combination ofseveral different peroxycarboxylic acids.

In an embodiment, the composition of the invention utilizes acombination of several different peroxycarboxylic acids. According toone embodiment, the composition includes one or more small C₂-C₄peroxycarboxylic acids, one or more large C₈-C₁₂ peroxycarboxylic acids,one or more ester peroxycarboxylic acids, one or more alkyl esterperoxycarboxylic acids, and/or one or more mono- or di-peroxycarboxylicacid having up to 12 carbon atoms. According to a further embodiment,the peroxycarboxylic acid has from 2 to 12 carbon atoms. According to anembodiment, the peroxycarboxylic acids include peroxyacetic acid (POAA)(or peracetic acid having the formula CH₃COOOH) and/or peroxyoctanoicacid (POOA) (or peroctanoic acid having the formula, for example, ofn-peroxyoctanoic acid: CH₃(CH₂)₆COOOH).

In an embodiment, the composition of the invention includes an esterperoxycarboxylic acid. As used herein, ester peroxycarboxylic acidrefers to a molecule having the formula:

R1 and R2 can independently be any of a wide variety of organic groups(e.g. alkyl, linear or cyclic, aromatic or saturated) or substitutedorganic groups (e.g., with one or more heteroatoms or organic groups).Ester peroxycarboxylic acid can be made using methods typically employedfor producing peroxycarboxylic acid, such as incubating thecorresponding ester carboxylic acid with an oxidizing agent, e.g.,hydrogen peroxide.

Alkyl esterperoxycarboxylic acids useful in this invention includemonomethyl monoperoxyoxalie acid, monomethyl monoperoxymalonic acid,monomethyl monoperoxysuccinic acid, monomethyl monoperoxyglutaric acid,monomethyl monoperoxyadipic acid, monomethyl monoperoxypimelic acid,monomethyl monoperoxysuberic acid, and monomethyl monoperoxysebacicacid; mono ethyl monoperoxyoxalic acid, mono ethyl monoperoxymalonicacid, monoethyl monoperoxysuccinic acid, mono ethyl monoperoxyglutaricacid, mono ethyl monoperoxyadipic acid, mono ethyl monoperoxypimelicacid, mono ethyl monoperoxysuberic acid, and monoethyl monoperoxysebacicacid; monopropyl monoperoxyoxalic acid, monopropyl monoperoxymalonicacid, monopropyl monoperoxysuccinic acid, monopropyl monoperoxyglutaricacid, monopropyl monoperoxyadipic acid, monopropyl monoperoxypimelicacid, monopropyl monoperoxysuberic acid, and monopropy Imonoperoxysebacic acid, in which propyl can be n- or isopropyl; andmonobutyl monoperoxyoxalic acid, monobutyl monoperoxymalonic acid,monobutyl monoperoxysuccinic acid, monobutyl monoperoxyglutaric acid,monobutyl monoperoxyadipic acid, monobutyl monoperoxypimelic acid,monobutyl monoperoxysuberic acid, and monobutyl monoperoxysebacic acid,in which butyl can be n-, iso-, or t-butyl.

Further description of suitable alkyl ester peroxycarboxylic acids andester peroxycarboxylic acids according to the invention is included inU.S. Pat. Nos. 7,816,555 and 7,622,606, both entitled “PeroxycarboxylicAcid Compositions with Reduced Odor,” hereby expressly incorporatedherein in its entirety by reference, including without limitation alldrawings and chemical structures contained therein.

In some embodiments of the invention at least one sulfoperoxycarboxylicacid is employed. Sulfoperoxycarboxylic acids, also referred to hereinas sulfonated peracids, may also be used according to the invention andare understood to include the peroxycarboxylic acid form of a sulfonatedcarboxylic acid. In some embodiments, the sulfonated peracids of thepresent invention are mid-chain sulfonated peracids, referring to aperacid compound that includes a sulfonate group attached to a carbonthat is at least one carbon (e.g., the three position or further) fromthe carbon of the percarboxylic acid group in the carbon backbone of thepercarboxylic acid chain, wherein the at least one carbon is not in theterminal position. As used herein, the term “terminal position,” refersto the carbon on the carbon backbone chain of a percarboxylic acid thatis furthest from the percarboxyl group.

According to an embodiment of the invention, sulfoperoxycarboxylic acidshave the following general formula:

wherein R₁ is hydrogen, or a substituted or unsubstituted alkyl group;R₂ is a substituted or unsubstituted alkyl group; X is hydrogen, acationic group, or an ester forming moiety; or salts or esters thereof.

In some embodiments, R₁ is a substituted or unsubstituted C_(m) alkylgroup; X is hydrogen a cationic group, or an ester forming moiety; R₂ isa substituted or unsubstituted C_(n) alkyl group; m=1 to 10; n=1 to 10;and m+n is less than 18, or salts, esters or mixtures thereof. In someembodiments, R₁ is hydrogen. In other embodiments, R₁ is a substitutedor unsubstituted alkyl group. In some embodiments, R₁ is a substitutedor unsubstituted alkyl group that does not include a cyclic alkyl group.In some embodiments, R₁ is a substituted alkyl group. In someembodiments, R₁ is an unsubstituted C₁-C₉ alkyl group. In someembodiments, R₁ is an unsubstituted C₇ or C₈ alkyl. In otherembodiments, R₁ is a substituted C₈-C₁₀ alkyl group. In someembodiments, R₁ is a substituted C₈-C₁₀ alkyl group is substituted withat least 1, or at least 2 hydroxyl groups. In still yet otherembodiments, R₁ is a substituted C₁-C₉ alkyl group. In some embodiments,R₁ is a substituted C₁-C₉ substituted alkyl group is substituted with atleast 1 SO₃H group. In other embodiments, R₁ is a C₉-C₁₀ substitutedalkyl group. In some embodiments, R₁ is a substituted C₉-C₁₀ alkyl groupwherein at least two of the carbons on the carbon backbone form aheterocyclic group. In some embodiments, the heterocyclic group is anepoxide group.

In further embodiments, R₂ is a substituted C₁-C₁₀ alkyl group. In someembodiments, R₂ is a substituted C₈-C₁₀ alkyl. In some embodiments, R₂is an unsubstituted C₆-C₉ alkyl. In other embodiments, R₂ is a C₈-C₁₀alkyl group substituted with at least one hydroxyl group. In someembodiments, R₂ is a C₁₀ alkyl group substituted with at least twohydroxyl groups. In other embodiments, R₂ is a C₈ alkyl groupsubstituted with at least one SO₃H group. In some embodiments, R₂ is asubstituted C₉ group, wherein at least two of the carbons on the carbonbackbone form a heterocyclic group. In some embodiments, theheterocyclic group is an epoxide group. In some embodiments, R₁ is aC₈-C₉ substituted or unsubstituted alkyl, and R₂ is a C₇-C₈ substitutedor unsubstituted alkyl.

Additional sulfoperoxycarboxylic acids suitable for use in the peracidcompositions of the invention include, for example, the following and/orany salts, esters and mixtures thereof:

Further description of suitable sulfoperoxycarboxylic acids, and methodsof making the same, according to the invention are included in U.S.patent application Ser. Nos. 13/290,355, 12/568,493 and Ser. No.12/413,179, entitled “Sulfoperoxycarboxylic Acids, Their Preparation andMethods of Use as Bleaching and Antimicrobial Agents,” hereby expresslyincorporated herein in its entirety by reference, including withoutlimitation all drawings and chemical structures contained therein.

In some embodiments of the invention at least one carboxylic acid isemployed in the peroxycarboxylic acid compositions. Generally,carboxylic acids have the formula R—COOH wherein the R can represent anynumber of different groups including aliphatic groups, alicyclic groups,aromatic groups, heterocyclic groups, and ester groups, such as alkylester groups, all of which can be saturated or unsaturated and/orsubstituted or unsubstituted. Carboxylic acids can have one, two, three,or more carboxyl groups.

Preferred ester groups include aliphatic ester groups, such asR₁OC(O)R₂— where each of R₁ and R₂ can be aliphatic, preferably alkyl,groups described above for R. Preferably R₁ and R₂ are eachindependently small alkyl groups, such as alkyl groups with 1 to 4carbon atoms.

The composition of the invention can employ carboxylic acids containingas many as 22 carbon atoms. Examples of suitable carboxylic acidsinclude formic, acetic, propionic, butanoic, pentanoic, hexanoic,heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, lactic,maleic, ascorbic, citric, hydroxyacetic (glycolic), neopentanoic,neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic,pimelic suberic, and sebacic acid. Examples of suitable alkyl estercarboxylic acids include monomethyl oxalic acid, monomethyl malonicacid, monomethyl succinic acid, monomethyl glutaric acid, monomethyladipic acid, monomethyl pimelic acid, monomethyl suberic acid, andmonomethyl sebacic acid; monoethyl oxalic acid, monoethyl malonic acid,monoethyl succinic acid, monoethyl glutaric acid, monoethyl adipic acid,monoethyl pimelic acid, monoethyl suberic acid, and monoethyl sebacicacid; monopropyl oxalic acid, monopropyl malonic acid, monopropylsuccinic acid, monopropyl glutaric acid, monopropyl adipic acid,monopropyl pimelic acid, monopropyl suberic acid, and monopropyl sebacicacid, in which propyl can be n- or isopropyl; and monobutyl oxalic acid,monobutyl malonic acid, monobutyl succinic acid, monobutyl glutaricacid, monobutyl adipic acid, monobutyl pimelic acid, monobutyl subericacid, and monobutyl sebacic acid, in which butyl can be n-, iso-, ort-butyl.

In some embodiments, the carboxylic acid for use with the compositionsof the present invention is a C₂ to C₁₂ carboxylic acid. In someembodiments, the carboxylic acid for use with the compositions of thepresent invention is a C₅ to C₁₁ carboxylic acid. In some embodiments,the carboxylic acid for use with the compositions of the presentinvention is a C₁ to C₄ carboxylic acid. Examples of suitable carboxylicacids include, but are not limited to, formic, acetic, propionic,butanoic, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic,undecanoic, dodecanoic, as well as their branched isomers, lactic,maleic, ascorbic, citric, hydroxyacetic, neopentanoic, neoheptanoic,neodecanoic, oxalic, malonic, succinic, glutaric, adipic, pimelic subricacid, and mixtures thereof. Carboxylic acids that are generally usefulinclude ester carboxylic acids, such as alkyl ester carboxylic acids.

In some embodiments, the compositions of the present invention include acombination of peroxycarboxylic acids, sulfoperoxycarboxylic acidsand/or carboxylic acids. According to an embodiment, the compositions ofthe present invention include at least one sulfoperoxycarboxylic acidand at least one carboxylic and/or percarboxylic acid. In someembodiments, the compositions of the present invention include at leasttwo, at least three, or at least four or more carboxylic and/orperoxycarboxylic acids.

The chemical structures herein, including the peroxycarboxylic acids,are drawn according to the conventional standards known in the art.Thus, where an atom, such as a carbon atom, as drawn appears to have anunsatisfied valency, then that valency is assumed to be satisfied by ahydrogen atom, even though that hydrogen atom is not necessarilyexplicitly drawn. The structures of some of the compounds of thisinvention include stereogenic carbon atoms. It is to be understood thatisomers arising from such asymmetry (e.g., all enantiomers anddiastereomers) are included within the scope of this invention unlessindicated otherwise. That is, unless otherwise stipulated, any chiralcarbon center may be of either (R)- or (S)-stereochemistry. Such isomerscan be obtained in substantially pure form by classical separationtechniques and by stereochemically-controlled synthesis. Furthermore,alkenes can include either the E- or Z-geometry, where appropriate. Inaddition, the compounds of the present invention may exist in unsolvatedas well as solvated forms with acceptable solvents such as water, THF,ethanol, and the like. In general, the solvated forms are consideredequivalent to the unsolvated forms for the purposes of the presentinvention.

The amount of peroxycarboxylic acid in use and concentrate compositionscan range up to the limits at which the peroxycarboxylic acid can bedissolved or suspended in the composition. Preferably, theperoxycarboxylic acid is present in a use or concentrate composition ata concentration of from about 0.0001 to about 50% by weight, preferablyfrom about 1 to about 50% by weight, from about 10 to about 50% byweight and from about 15 to about 50% by weight. Typically usecompositions include at least about 0.1 wt-%, preferably at least about1 wt-% peroxycarboxylic acid according to the invention. It is to beunderstood that all ranges and values between these ranges and valuesare encompassed by the present invention.

Making the Peroxycarboxylic Acids

Exemplary methods and apparatus for making peroxycarboxylic acids aredisclosed in U.S. Pat. No. 7,547,421 and U.S. patent application Ser.No. 12/430,523, both entitled “Apparatus and Method for Making aPeroxycarboxylic Acid,” hereby expressly incorporated herein in itsentirety by reference. These and other known methods and apparatus formaking the particular peroxycarboxylic acids and/orsulfoperoxycarboxylic acids according to the invention are includedwithin the scope of the invention.

In some embodiments, the starting material for the preparation of theperoxycarboxylic acids of the compositions is a fatty acid, such as asulfonated fatty acid. In some embodiments, the percarboxylic acids ofthe present invention are formed from commercially available fattyacids. According to some embodiments the percarboxylic acids of thepresent invention are formed from sulfonated fatty acids. In otherembodiments, the compounds of the present invention are formed fromcommercially available non-sulfonated fatty acids, which can besulfonated. In some embodiments, the starting fatty acid will besulfonated prior to conversion to a peroxycarboxylic acid. In otherembodiments, the starting fatty acid will be sulfonated at the same timeor after the formation of the peroxycarboxylic acid. Sulfonated fattyacids suitable for use in forming compounds of the present inventioninclude, but are not limited to, 11-sulfoundecanoic acid,10,11-disulfoundecanoic acid, sulfonated oleic acid, sulfonated linoleicacid, sulfonated palmitoleic acid and sulfonated stearic acid.

Depending upon the starting fatty acid for the preparation of theperoxycarboxylic acids of the compositions, a mixture of compounds areincluded in the compositions of the present invention. For example,according to the embodiment of the invention using a sulfonated oleicacid starting material which may contain more than one form of thesulfonated oleic acid as it is not chemically pure, the formedperoxysulfonated oleic acid can include a mixture of sulfoperoxyacidcompounds. According to this embodiment of the invention, thesulfoperoxyacids can be formed using a variety of reaction mechanisms,including for example, direct acid catalyzed equilibrium action ofhydrogen peroxide with the starting materials.

In some aspects, at ambient conditions, the reaction to make theperoxycarboxylic acid compositions may take a week or more to reach thedesirable concentrations of peroxycarboxylic acid at equilibrium. Inother aspects, at more favorable conditions, such as those describedemploying DDBSA and/or sulfuric acid in a mixture, the maximumperoxycarboxylic concentration may be reached in about 60 minutes orwithin a few hours. One skilled in the art will ascertain the variousmodifications to the conditions of the peroxycarboxylic acid reactionsin order to obtain the desirable concentrations within a particularamount of time.

Alcohols

A variety of alcohols may be used in the peroxycarboxylic acidcompositions according to the invention to remove malodorous, lowmolecular weight carboxylic acids through esterification. The alcohol ispreferably a lower chain alcohol such as a C₂-C₆ or a C₂-C₄ alcohol.Alcohols having different concentrations may be employed according tothe invention. The alcohol may also be a mixture of alcohols.Accordingly, the composition may contain one alcohol, or a mixture oftwo or more alcohols.

Examples of suitable alcohols for use in the peroxycarboxylic acidcompositions according to the invention include methanol, ethanol,propanols, butanols, benzyl alcohol, nonanols and the like. The alcoholis preferably ethanol, providing a pleasant, fruity odor and a costeffective solution to the problem solved by the present invention.According to a further embodiment, ethanol provides unreacted residueshaving a favorable toxicity profile.

According to the present invention, formulation of the peroxycarboxylicacid compounds including an alcohol, such as ethanol, results in apleasant ester-like odor in the formulation within several hours ofadding ethanol and/or the other alcohols. Although not intending to belimited according to a particular theory of the invention, the alcoholresults in either significant esterification of the various short chaincarboxylic acids or at least a thorough masking of those odors.

The alcohol is preferably present in the peracid composition in anamount from about 0.1 wt-% to about 20 wt-%, from about 1 wt-% to about10 wt-% or from about 1 wt-% to about 5 wt-% alcohol. The amount ofalcohol in the peracid compositions according to the invention may varydepending upon the formulation of a concentration or a use solution. Incertain embodiments, a concentrate composition may be diluted by afactor of from about 16:1 to about 1000:1, resulting in useconcentrations of the alcohol from about 5 ppm to about 1,000 ppm. It isto be understood that all ranges and values between these ranges andvalues are encompassed by the present invention.

Oxidizing Agents

In some aspects of the invention, the peroxycarboxylic acid compositionsinclude at least one oxidizing agent. When present in theperoxycarboxylic acid compositions, any of a variety of oxidizing agentsmay be employed, for example, hydrogen peroxide. The oxidizing agent canbe present at an amount effective to convert a fatty acid, such as acarboxylic acid or a sulfonated carboxylic acid to a peroxycarboxylicacid or a sulfonated peroxycarboxylic acid. In some embodiments, theoxidizing agent can also have antimicrobial activity. In otherembodiments, the oxidizing agent is present in an amount insufficient toexhibit antimicrobial activity.

Examples of inorganic oxidizing agents include the following types ofcompounds or sources of these compounds, or alkali metal salts includingthese types of compounds, or forming an adduct therewith: hydrogenperoxide, urea-hydrogen peroxide complexes or hydrogen peroxide donorsof: group 1 (IA) oxidizing agents, for example lithium peroxide, sodiumperoxide; group 2 (IIA) oxidizing agents, for example magnesiumperoxide, calcium peroxide, strontium peroxide, barium peroxide; group12 (IIB) oxidizing agents, for example zinc peroxide; group 13 (IIIA)oxidizing agents, for example boron compounds, such as perborates, forexample sodium perborate hexahydrate of the formula Na₂[B₂(O₂)₂(OH)₄]₆H₂2O (also called sodium perborate tetrahydrate); sodiumperoxyborate tetrahydrate of the formula Na₂B₂(O₂)₂[(OH)₄]₄H₂O (alsocalled sodium perborate trihydrate); sodium peroxyborate of the formulaNa₂[B₂(O₂)₂(OH).₄] (also called sodium perborate monohydrate); group 14(IVA) oxidizing agents, for example persilicates and peroxycarbonates,which are also called percarbonates, such as persilicates orperoxycarbonates of alkali metals; group 15 (VA) oxidizing agents, forexample peroxynitrous acid and its salts; peroxyphosphoric acids andtheir salts, for example, perphosphates; group 16 (VIA) oxidizingagents, for example peroxysulfuric acids and their salts, such asperoxymonosulfuric and peroxydisulfuric acids, and their salts, such aspersulfates, for example, sodium persulfate; and group VIIa oxidizingagents such as sodium periodate, potassium perchlorate. Other activeinorganic oxygen compounds can include transition metal peroxides; andother such peroxygen compounds, and mixtures thereof.

In some embodiments, the compositions of the present invention employone or more of the inorganic oxidizing agents listed above. Suitableinorganic oxidizing agents include ozone, hydrogen peroxide, hydrogenperoxide adduct, group IIIA oxidizing agent, or hydrogen peroxide donorsof group VIA oxidizing agent, group VA oxidizing agent, group VIIAoxidizing agent, or mixtures thereof. Suitable examples of suchinorganic oxidizing agents include percarbonate, perborate, persulfate,perphosphate, persilicate, or mixtures thereof.

The peroxycarboxylic acid compositions preferably include a hydrogenperoxide constituent. Beneficially, hydrogen peroxide in combinationwith the peroxycarboxylic acids provides certain antimicrobial actionsagainst microorganisms. Additionally, hydrogen peroxide can provide aneffervescent action which can irrigate any surface to which it isapplied. Hydrogen peroxide works with a mechanical flushing action onceapplied which further cleans the surface. An additional advantage ofhydrogen peroxide is the food compatibility of this composition upon useand decomposition. For example, combinations of peroxyacetic acid,peroxyoctanoic acid, and hydrogen peroxide result in acetic acid,octanoic acid, water, and oxygen upon decomposition, all of which arefood product compatible and do not adversely affect an apparatus,handling or processing, or other surfaces to which the peroxycarboxylicacid composition is applied.

In some embodiments, the compositions of the present invention includeabout 0.5 wt-% oxidizing agent to about 90 wt-% oxidizing agent. Inother embodiments, the compositions of the present invention includeabout 1 wt % to about 80 wt % oxidizing agent. In some embodiments, thecompositions of the invention include about 10 wt-% to about 80 wt-%oxidizing agent. It is to be understood that all ranges and valuesbetween these ranges and values are encompassed by the presentinvention.

Surfactant

In some aspects of the invention, the peroxycarboxylic acid compositionsinclude at least one surfactant. Surfactants are preferably included inthe peroxycarboxylic acid compositions to increase solubility of theperoxycarboxylic acid or to maintain the pH of the composition.According to an embodiment of the invention, the surfactant is ahydrotrope coupler or solubilizer, which can be used to ensure that thecomposition remains phase stable and in a single highly active aqueousform. Such hydrotrope solubilizers or couplers can be used atconcentrations that maintain phase stability but do not result inunwanted compositional interaction.

Surfactants particularly suitable for use with the compositions of thepresent invention include, but are not limited to, nonionic surfactants,anionic surfactants, amphoteric surfactants and zwitterionicsurfactants. Preferably, anionic surfactants are employed with theperacid compositions of the invention. Exemplary surfactants that can beused are commercially available from a number of sources. For adiscussion of surfactants, see Kirk-Othmer, Encyclopedia of ChemicalTechnology, Third Edition, volume 8, pages 900-912.

According to a preferred embodiment of the invention, the surfactant isan acidic anionic surfactant. According to a further embodiment, thesurfactant is an antimicrobial agent. Exemplary surfactant, hydrotropesolubilizers include anionic surfactants such as an alkyl sulfate, anaryl sulfonate, an alkyl or alkane sulfonate, a linear alkyl benzene ornaphthalene sulfonate, a secondary alkane sulfonate, alkyl ether sulfateor sulfonate, an alkyl phosphate or phosphonate, dialkyl sulfosuccinicacid ester, sugar esters (e.g., sorbitan esters) and a C₈₋₁₀ alkylglucoside.

In some embodiments, the compositions of the present invention includesfrom about 1 wt-% to about 80 wt-% of a surfactant. In other embodimentsthe compositions of the present invention include from about 1 wt-% toabout 50 wt-% of a surfactant. In additional embodiments, thecompositions of the present invention include from about 1 wt-% to about10 wt-% of a surfactant. In further embodiments, the compositions of thepresent invention include about 10 ppm to about 10,000 ppm of asurfactant. In further embodiments, the compositions of the presentinvention include about 10 ppm to about 100 ppm of a surfactant. It isto be understood that all ranges and values between these ranges andvalues are encompassed by the present invention.

Nonionic Surfactants

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers, such as the Pluronic andreverse Pluronic surfactants; alcohol alkoxylates; and capped alcoholalkoxylates, such as Plurafac LF221 and Tegoten EC11; mixtures thereof,or the like.

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents are another classof nonionic surfactant useful in compositions of the present invention.Semi-polar nonionic surfactants include the amine oxides, phosphineoxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkyleneor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20. An amine oxide can be generated from thecorresponding amine and an oxidizing agent, such as hydrogen peroxide.

Useful water soluble amine oxide surfactants are selected from theoctyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(loweralkyl)amine oxides, specific examples of which are octyldimethylamineoxide, nonyldimethylamine oxide, decyldimethylamine oxide,undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Anionic Surfactants

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy)ether sulfates and aromaticpoly(ethyleneoxy)sulfates such as the sulfates or condensation productsof ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylenegroups per molecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, and the like. Such carboxylates include alkylethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps (e.g. alkyl carboxyls). Secondarycarboxylates useful in the present compositions include those whichcontain a carboxyl unit connected to a secondary carbon. The secondarycarbon can be in a ring structure, e.g. as in p-octyl benzoic acid, oras in alkyl-substituted cyclohexyl carboxylates. The secondarycarboxylate surfactants typically contain no ether linkages, no esterlinkages and no hydroxyl groups. Further, they typically lack nitrogenatoms in the head-group (amphiphilic portion). Suitable secondary soapsurfactants typically contain 11-13 total carbon atoms, although morecarbons atoms (e.g., up to 16) can be present. Suitable carboxylatesalso include acylamino acids (and salts), such as acylgluamates, acylpeptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyltaurates and fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:

R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X

in which R is a C₈ to C₂₂ alkyl group or

in which R₁ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₈-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R₁ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R₁ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form.

Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphate, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989), which is herein incorporated by reference in its entirety. Thefirst class includes acyl/dialkyl ethylenediamine derivatives (e.g.2-alkyl hydroxyethyl imidazoline derivatives) and their salts. Thesecond class includes N-alkylamino acids and their salts. Someamphoteric surfactants can be envisioned as fitting into both classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation—for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Exemplary suitable amphoteric surfactants include long chain imidazolederivatives, including carboxymethylated compounds (glycinates) whichare frequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants. These and other amphoteric surfactants are furtherdescribed in U.S. patent application Ser. No. 12/568,493, entitled“Sulfoperoxycarboxylic Acids, Their Preparation and Methods of Use asBleaching and Antimicrobial Agents,” hereby expressly incorporatedherein in its entirety by reference.

Long chain imidazole derivatives having application in the presentinvention generally have the general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate,Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, andCocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants.

Additionally suitable amphoteric surfactants include long chainN-alkylamino acids which are readily prepared by reaction RNH₂, in whichR=C₈-C₈ straight or branched chain alkyl, fatty amines with halogenatedcarboxylic acids. Alkylation of the primary amino groups of an aminoacid leads to secondary and tertiary amines. Alkyl substituents may haveadditional amino groups that provide more than one reactive nitrogencenter. Most commercial N-alkylamine acids are alkyl derivatives ofbeta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercialN-alkylamino acid ampholytes having application in this inventioninclude alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ and RNHC₂H₄COOM.In an embodiment, R can be an acyclic hydrophobic group containing fromabout 8 to about 18 carbon atoms, and M is a cation to neutralize thecharge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N+(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N+(CH₂—CO₂Na)₂—CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename Miranol™ FBS from Rhodia Inc.(Cranbury, N.J.). Another suitable coconut derived amphoteric surfactantwith the chemical name disodium cocoampho diacetate is sold under thetradename Mirataine™ JCHA, also from Rhodia Inc.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975 and further examples are given in “SurfaceActive Agents and Detergents” (Vol. I and II by Schwartz, Perry andBerch), each of which are hereby expressly incorporated herein in itsentirety by reference.

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

A general formula for these compounds is:

wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; andS[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said detergent surfactants can be straightor branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄acylamidohexyldiethyl betaine; 4-C₁₄₋₁₆acylmethylamidodiethylammonio-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethylbetaine; andC₁₂₋₁₆ acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds havingthe formula (R(R¹)₂N⁺R²SO³⁻, in which R is a C₆-C₁₈ hydrocarbyl group,each R¹ is typically a C₁-C₃ alkyl, e.g. methyl, and R² is a C₁-C₆hydrocarbyl group, e.g. a C₁-C₃ alkylene or hydroxyalkylene group.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated in their entirety.

Adjuvants—Other Additional Ingredients

In some embodiments, the compositions of the present invention caninclude other additional ingredients. Additional ingredients suitablefor use with the compositions of the present invention include, but arenot limited to, acidulants, stabilizing agents, e.g., chelating agents,sequestrants and/or crystallization inhibitors, buffers, detergents,wetting agents, defoaming agents, thickeners, foaming agents, hydrogenperoxide reducing agents (e.g. catalyase enzymes), solidificationagents, aesthetic enhancing agents (i.e., colorants, odorants, orperfumes) and other cleaning agents. These additional ingredients can bepreformulated with the compositions of the invention or added to thesystem before, after, or substantially simultaneously with the additionof the compositions of the present invention. Additionally, thecompositions can be used in conjunction with one or more conventionalcleaning agents, e.g., an alkaline detergent.

Acidulants

In some embodiments, the compositions of the present invention includean acidulant. The acidulant can act as a catalyst for conversion ofcarboxylic acid to peroxycarboxylic acid or ester formation. Theacidulant can be effective to form a concentrate composition with pH ofabout 1 or less. The acidulant can be effective to form a usecomposition with pH of about 5, about 5 or less, about 4, about 4 orless, about 3, about 3 or less, about 2, about 2 or less, or the like.In some embodiments, an acidulant can be used to lower the pH of analkaline cleaning solution to a pH of about 10, about 10 or less, about9, about 9 or less, about 8, about 8 or less, about 7, about 7 or less,about 6, or about 6 or less. In an embodiment, the acidulant includes aninorganic acid. Suitable inorganic acids include, but are not limitedto, sulfuric acid, sodium bisulfate, phosphoric acid, nitric acid,hydrochloric acid. In some embodiments, the acidulant includes anorganic acid. Suitable organic acids include, but are not limited to,methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid,butane sulfonic acid, xylene sulfonic acid, benzene sulfonic acid,formic acid, acetic acid, mono, di, or tri-halocarboyxlic acids,picolinic acid, dipicolinic acid, and mixtures thereof. In someembodiments, the compositions of the present invention are free orsubstantially free of a phosphorous based acid.

In some embodiments, acidulant selected can also function as astabilizing agent. Thus, the compositions of the present invention canbe substantially free of an additional stabilizing agent.

In certain embodiments, the present composition includes about 0.5 toabout 80 wt-% acidulant, about 1 to about 50 wt-%, about 5 to about 30wt-% acidulant, or about 7 to about 14 wt-% acidulant. It is to beunderstood that all values and ranges between these values and rangesare encompassed by the compositions of the present invention.

Stabilizing Agents

In some embodiments, the compositions of the present invention includeone or more stabilizing agents. The stabilizing agents can be used, forexample, to stabilize the peracid and hydrogen peroxide and prevent thepremature oxidation of this constituent within the composition of theinvention. In some embodiments, an acidic stabilizing agent can be used.Thus, in some embodiments, the compositions of the present invention canbe substantially free of an additional acidulant. Suitable stabilizingagents include, for example, chelating agents or sequestrants. Suitablesequestrants include, but are not limited to, organic chelatingcompounds that sequester metal ions in solution, particularly transitionmetal ions. Such sequestrants include organic amino- orhydroxy-polyphosphonic acid complexing agents (either in acid or solublesalt forms), carboxylic acids (e.g., polymeric polycarboxylate),hydroxycarboxylic acids, aminocarboxylic acids, or heterocycliccarboxylic acids, e.g., pyridine-2,6-dicarboxylic acid (dipicolinicacid).

In some embodiments, the compositions of the present invention includedipicolinic acid as a stabilizing agent. Compositions includingdipicolinic acid can be formulated to be free or substantially free ofphosphorous. It has also been observed that the inclusion of dipicolinicacid in a composition of the present invention aids in achieving thephase stability of the compositions, compared to other conventionalstabilizing agents, e. 1-hydroxy ethylidene-1,1-diphosphonic acid(CH₃C(PO₃H₂)₂OH) (HEDP).

In other embodiments, the sequestrant can be or include phosphonic acidor phosphonate salt. Suitable phosphonic acids and phosphonate saltsinclude HEDP; ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; picolinic, dipicolinic acid ormixtures thereof. In some embodiments, organic phosphonates, e.g., HEDPare included in the compositions of the present invention.

Commercially available food additive chelating agents includephosphonates sold under the trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂2PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM.

The sequestrant can be or include aminocarboxylic acid type sequestrant.Suitable aminocarboxylic acid type sequestrants include the acids oralkali metal salts thereof, e.g., amino acetates and saltsthereofuitable aminocarboxylates include N-hydroxyethylaminodiaceticacid; hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid(NTA); ethylenediaminetetraacetic acid (EDTA);N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof.

The sequestrant can be or include a polycarboxylate. Suitablepolycarboxylates include, for example, polyacrylic acid, maleic/olefincopolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylicacid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzedpolymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile,hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymaleic acid,polyfumaric acid, copolymers of acrylic and itaconic acid, phosphinopolycarboxylate, acid or salt forms thereof, mixtures thereof, and thelike.

In certain embodiments, the present composition includes about 0.01 toabout 10 wt-% stabilizing agent, about 0.4 to about 4 wt-% stabilizingagent, about 0.6 to about 3 wt-% stabilizing agent, about 1 to about 2wt-% stabilizing agent. It is to be understood that all values andranges within these values and ranges are encompassed by the presentinvention.

Wetting or Defoaming Agents

Also useful in the compositions of the invention are wetting anddefoaming agents.

Wetting agents function to increase the surface contact or penetrationactivity of the antimicrobial composition of the invention. Wettingagents which can be used in the composition of the invention include anyof those constituents known within the art to raise the surface activityof the composition of the invention.

Generally, defoamers which can be used in accordance with the inventioninclude silica and silicones; aliphatic acids or esters; alcohols;sulfates or sulfonates; amines or amides; halogenated compounds such asfluorochlorohydrocarbons; vegetable oils, waxes, mineral oils as well astheir sulfonated or sulfated derivatives; fatty acids and/or their soapssuch as alkali, alkaline earth metal soaps; and phosphates and phosphateesters such as alkyl and alkaline diphosphates, and tributyl phosphatesamong others; and mixtures thereof.

In some embodiments, the compositions of the present invention caninclude antifoaming agents or defoamers which are of food grade qualitygiven the application of the method of the invention. To this end, oneof the more effective antifoaming agents includes silicones. Siliconessuch as dimethyl silicone, glycol polysiloxane, methylphenolpolysiloxane, trialkyl or tetralkyl silanes, hydrophobic silicadefoamers and mixtures thereof can all be used in defoamingapplications. Commercial defoamers commonly available include siliconessuch as Ardefoam® from Armour Industrial Chemical Company which is asilicone bound in an organic emulsion; Foam Kill® or Kresseo® availablefrom Kirusable Chemical Company which are silicone and non-silicone typedefoamers as well as silicone esters; and Anti-Foam A® and DC-200 fromDow Corning Corporation which are both food grade type silicones amongothers. These defoamers can be present at a concentration range fromabout 0.01 wt-% to 20 wt-%, from about 0.01 wt-% to 5 wt-%, or fromabout 0.01 wt-% to about 1 wt-%. It is to be understood that all valuesand ranges within these values and ranges are encompassed by the presentinvention.

Thickening or Gelling Agents

The compositions of the present invention can include any of a varietyof known thickeners. Suitable thickeners include natural gums such asxanthan gum, guar gum, or other gums from plant mucilage; polysaccharidebased thickeners, such as alginates, starches, and cellulosic polymers(e.g., carboxymethyl cellulose); polyacrylates thickeners; andhydrocolloid thickeners, such as pectin. In an embodiment, the thickenerdoes not leave contaminating residue on the surface of an object. Forexample, the thickeners or gelling agents can be compatible with food orother sensitive products in contact areas. Generally, the concentrationof thickener employed in the present compositions or methods will bedictated by the desired viscosity within the final composition. However,as a general guideline, the viscosity of thickener within the presentcomposition ranges from about 0.1 wt-% to about 5 wt-%, from about 0.1wt-% to about 1.0 wt-%, or from about 0.1 wt-% to about 0.5 wt-%. It isto be understood that all values and ranges within these values andranges are encompassed by the present invention.

Solidification Agent

The present compositions can include a solidification agent, which canparticipate in maintaining the compositions in a solid form. In someembodiments, the solidification agent can form and/or maintain thecomposition as a solid. In other embodiments, the solidification agentcan solidify the composition without unacceptably detracting from theeventual release of the sulfonated peroxycarboxylic acid. Thesolidification agent can include, for example, an organic or inorganicsolid compound having a neutral inert character or making a functional,stabilizing or detersive contribution to the present composition.Suitable solidification agents include solid polyethylene glycol (PEG),solid polypropylene glycol, solid EO/PO block copolymer, amide, urea(also known as carbamide), nonionic surfactant (which can be employedwith a coupler), anionic surfactant, starch that has been madewater-soluble (e.g., through an acid or alkaline treatment process),cellulose that has been made water-soluble, inorganic agent, poly(maleicanhydride/methyl vinyl ether), polymethacrylic acid, other generallyfunctional or inert materials with high melting points, mixturesthereof, and the like.

Suitable glycol solidification agents include a solid polyethyleneglycol or a solid polypropylene glycol, which can, for example, havemolecular weight of about 1,400 to about 30,000. In certain embodiments,the solidification agent includes or is solid PEG, for example PEG 1500up to PEG 20,000. In certain embodiments, the PEG includes PEG 1450, PEG3350, PEG 4500, PEG 8000, PEG 20,000, and the like. Suitable solidpolyethylene glycols are commercially available from Union Carbide underthe tradename CARBOWAX™.

Suitable amide solidification agents include stearic monoethanolamide,lauric diethanolamide, stearic diethanolamide, stearic monoethanolamide, cocodiethylene amide, an alkylamide, mixtures thereof, and thelike. In an embodiment, the present composition can include glycol(e.g., PEG) and amide.

Suitable nonionic surfactant solidification agents include nonylphenolethoxylate, linear alkyl alcohol ethoxylate, ethylene oxide/propyleneoxide block copolymer, mixtures thereof, or the like. Suitable ethyleneoxide/propylene oxide block copolymers include those sold under thePluronic tradename (e.g., Pluronic 108 and Pluronic F68) andcommercially available from BASF Corporation. In some embodiments, thenonionic surfactant can be selected to be solid at room temperature orthe temperature at which the composition will be stored or used. Inother embodiments, the nonionic surfactant can be selected to havereduced aqueous solubility in combination with the coupling agent.Suitable couplers that can be employed with the nonionic surfactantsolidification agent include propylene glycol, polyethylene glycol,mixtures thereof, or the like.

Suitable anionic surfactant solidification agents include linear alkylbenzene sulfonate, alcohol sulfate, alcohol ether sulfate, alpha olefinsulfonate, mixtures thereof, and the like. In an embodiment, the anionicsurfactant solidification agent is or includes linear alkyl benzenesulfonate. In an embodiment, the anionic surfactant can be selected tobe solid at room temperature or the temperature at which the compositionwill be stored or used.

Suitable inorganic solidification agents include phosphate salt (e.g.,alkali metal phosphate), sulfate salt (e.g., magnesium sulfate, sodiumsulfate or sodium bisulfate), acetate salt (e.g., anhydrous sodiumacetate), Borates (e.g., sodium borate), Silicates (e.g., theprecipitated or fumed forms (e.g., Sipernat 50® available from Degussa),carbonate salt (e.g., calcium carbonate or sodium carbonate or theirlower hydrates), other known hydratable compounds, mixtures thereof, andthe like. In an embodiment, the inorganic solidification agent caninclude organic phosphonate compound and carbonate salt, such as anE-Form composition.

In some embodiments, the compositions of the present invention caninclude any agent or combination of agents that provide a requisitedegree of solidification and aqueous solubility can be included in thepresent compositions. In other embodiments, increasing the concentrationof the solidification agent in the present composition can tend toincrease the hardness of the composition. In yet other embodiments,decreasing the concentration of solidification agent can tend to loosenor soften the concentrate composition.

In some embodiments, the solidification agent can include any organic orinorganic compound that imparts a solid character to and/or controls thesoluble character of the present composition, for example, when placedin an aqueous environment. For example, a solidifying agent can providecontrolled dispensing if it has greater aqueous solubility compared toother ingredients in the composition. Urea can be one suchsolidification agent. By way of further example, for systems that canbenefit from less aqueous solubility or a slower rate of dissolution, anorganic nonionic or amide hardening agent may be appropriate.

In some embodiments, the compositions of the present invention caninclude a solidification agent that provides for convenient processingor manufacture of the present composition. For example, thesolidification agent can be selected to form a composition that canharden to a solid form under ambient temperatures of about 30 to about50° C. after mixing ceases and the mixture is dispensed from the mixingsystem, within about 1 minute to about 3 hours, or about 2 minutes toabout 2 hours, or about 5 minutes to about 1 hour.

The compositions of the present invention can include solidificationagent at any effective amount. The amount of solidification agentincluded in the present composition can vary according to the type ofcomposition, the ingredients of the composition, the intended use of thecomposition, the quantity of dispensing solution applied to the solidcomposition over time during use, the temperature of the dispensingsolution, the hardness of the dispensing solution, the physical size ofthe solid composition, the concentration of the other ingredients, theconcentration of the cleaning agent in the composition, and other likefactors. Suitable amounts can include about 1 to about 99 wt-%, about1.5 to about 85 wt-%, about 2 to about 80 wt-%, about 10 to about 45wt-%, about 15% to about 40 wt-%, about 20% to about 30 wt-%, about 30%to about 70 wt-%, about 40% to about 60 wt-%, up to about 50 wt-%, about40% to about 50 wt-%. It is to be understood that all values and rangeswithin these values and ranges are encompassed by the present invention.

Carrier

In some embodiments, the compositions of the present invention include acarrier. The carrier provides a medium which dissolves, suspends, orcarries the other components of the composition. For example, thecarrier can provide a medium for solubilization, suspension, orproduction of a sulfonated peroxycarboxylic acid and for forming anequilibrium mixture. The carrier can also function to deliver and wetthe composition of the invention on an object. To this end, the carriercan contain any component or components that can facilitate thesefunctions.

In some embodiments, the carrier includes primarily water which canpromote solubility and work as a medium for reaction and equilibrium.The carrier can include or be primarily an organic solvent, such assimple alkyl alcohols, e.g., ethanol, isopropanol, n-propanol, benzylalcohol, and the like. Polyols are also useful carriers, includingglycerol, sorbitol, and the like.

Suitable carriers include glycol ethers. Suitable glycol ethers includediethylene glycol n-butyl ether, diethylene glycol n-propyl ether,diethylene glycol ethyl ether, diethylene glycol methyl ether,diethylene glycol t-butyl ether, dipropylene glycol n-butyl ether,dipropylene glycol methyl ether, dipropylene glycol ethyl ether,dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether,ethylene glycol butyl ether, ethylene glycol propyl ether, ethyleneglycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methylether acetate, propylene glycol n-butyl ether, propylene glycol ethylether, propylene glycol methyl ether, propylene glycol n-propyl ether,tripropylene glycol methyl ether and tripropylene glycol n-butyl ether,ethylene glycol phenyl ether (commercially available as DOWANOL EPH™from Dow Chemical Co.), propylene glycol phenyl ether (commerciallyavailable as DOWANOL PPH™ from Dow Chemical Co.), and the like, ormixtures thereofdditional suitable commercially available glycol ethers(all of which are available from Union Carbide Corp.) includeButoxyethyl PROPASOL™, Butyl CARBITOL™ acetate, Butyl CARBITOL™, ButylCELLOSOLVE™ acetate, Butyl CELLOSOLVE™, Butyl DIPROPASOL™, ButylPROPASOL™, CARBITOL™ PM-600, CARBITOL™ Low Gravity, CELLOSOLVE™ acetate,CELLOSOLVE™, Ester EEP™, FILMER IBT™, Hexyl CARBITOL™, HexylCELLOSOLVE™, Methyl CARBITOL™, Methyl CELLOSOLVE™ acetate, MethylCELLOSOLVE™, Methyl DIPROPASOL™, Methyl PROPASOL™ acetate, MethylPROPASOL™, Propyl CARBITOL™, Propyl CELLOSOLVE™, Propyl DIPROPASOL™ andPropyl PROPASOL™.

In some embodiments, the carrier makes up a large portion of thecomposition of the invention and may be the balance of the compositionapart from the sulfonated peroxycarboxylic acid, oxidizing agent,additional ingredients, and the like. The carrier concentration and typewill depend upon the nature of the composition as a whole, theenvironmental storage, and method of application including concentrationof the sulfonated peroxycarboxylic acid, among other factors. Notablythe carrier should be chosen and used at a concentration which does notinhibit the efficacy of the peroxycarboxylic acid composition and itsintended use, e.g., bleaching, sanitizing, disinfecting.

In certain embodiments, the present composition includes about 5 toabout 90 wt-% carrier, about 10 to about 80 wt-% carrier, about 20 toabout 60 wt-% carrier, or about 30 to about 40 wt-% carrier. It is to beunderstood that all values and ranges between these values and rangesare encompassed by the present invention.

Use Compositions

The peroxycarboxylic acid compositions of the present invention includeboth concentrate compositions and use compositions. For example, aconcentrate composition can be diluted, for example with water, to forma use composition. In an embodiment, a concentrate composition can bediluted to a use solution before to application to an object. Primarilyfor reasons of economics, the concentrate can be marketed and an enduser can dilute the concentrate with water or an aqueous diluent to ause solution.

The level of active components in the concentrate composition isdependent on the intended dilution factor and the desired activity ofthe sulfonated peroxycarboxylic acid compound. Generally, a dilution ofabout 1 fluid ounce to about 10 gallons of water to about 10 fluidounces to about 1 gallon of water is used for aqueous compositions ofthe present invention. In some embodiments, higher use dilutions can beemployed if elevated use temperature or extended exposure time (greaterthan 30 seconds) can be employed. In the typical use locus, theconcentrate is diluted with a major proportion of water using commonlyavailable tap or service water mixing the materials at a dilution ratioof about 3 to about 40 ounces of concentrate per 100 gallons of water.

In some embodiments, such as use in laundry applications, theconcentrated compositions can be diluted at a dilution ratio of about0.1 g/L to about 100 g/L concentrate to diluent, about 0.5 g/L to about10.0 g/L concentrate to diluent, about 1.0 g/L to about 4.0 g/Lconcentrate to diluent, or about 1.0 g/L to about 2.0 g/L concentrate todiluent. In other embodiments, a use composition can include about 0.01to about 10 wt-% of a concentrate composition and about 90 to about99.99 wt-% diluent; or about 0.1 to about 1 wt-% of a concentratecomposition and about 99 to about 99.9 wt-% diluent. Amounts of aningredient in a use composition can be calculated from the amountslisted above for concentrate compositions and these dilution factors.

As one skilled in the art shall appreciate based on the disclosure ofthe present invention, the reduced-odor peracid compositions of theinvention can be formulated as a liquid concentrate composition and/oruse compositions. The peracid compositions of the present invention canalso be formulated as a gel, an aerosol, a gas, a wax, a solid, or apowder, or as a solution or suspension containing such a composition.

Methods of Use Employing Peracid Compositions

The present invention includes methods employing the reduced-odorantimicrobial peracid compositions. According to one embodiment of theinvention, the methods employ the antimicrobial or bleaching activity ofthe peracid of the compositions. The compositions of the presentinvention can be used as antimicrobial or bleaching compositions for avariety of substrates and surfaces, e.g., textiles and hard surfaces.The compositions of the present invention can also be used asantimicrobial, disinfectant and/or sanitizer compositions. Thecompositions of the present invention can also be used for production ofpolymers, including for example, epoxides. The compositions of thepresent invention can further be used in pulp and paper bleachingmethods having improved odors for the manufacturing methods.

In an aspect of the invention, the reduced-odor antimicrobial peracidcompositions provide at least substantially similar cleaning and/orantimicrobial performance in comparison to peracid compositions that donot employ an alcohol for the esterification reaction to remove short-to mid-chain length malodorous carboxylic acids according to theinvention. The compositions may be used for various applications, e.g.,food contact sanitizing, hard surface disinfection, and textiledisinfection. In some embodiments, compositions containing compounds ofthe present invention can be multipurpose. That is, the compositions ofthe present invention can, for example, act as both antimicrobials andbleaches. The compositions of the present invention can further act asdisinfection, a combination of disinfection and cleaning, virucidaltreatment and/or fungicidal treatment.

According to an embodiment of the invention, a method for reducing amicrobial population on a variety of surfaces, a method for reducing anodor, and a method for bleaching a variety of surfaces are provided. Themethods according to the invention can operate on an object, surface, orthe like, by contacting the object or surface with a reduced-odorperacid composition of the invention. As one skilled in the art shallascertain based upon the disclosure of the present invention, contactingcan include any of numerous methods for applying a composition, such asspraying the composition, immersing the object in the composition, foamor gel treating the object with the composition, or a combinationthereof.

The peracid compositions of the invention can be used for a variety ofdomestic or industrial applications. In an embodiment, the peracidcompositions can be used at manufacturing or processing sites handlingfoods and plant species. In further embodiments the compositions can beemployed for cleaning or sanitizing food processing equipment ormaterials; sanitizing food contact and nonfood contact hard surfaces,including as a delivery agent of available oxygen; aseptic and ESLbottle rinse applications; conveyor treatments; foam sanitizing fornonfood contact surfaces; fogging sanitization for rooms; nonfoodcontact packaging equipment; bacteriophage control when applied topre-cleaned surfaces; sterilization of manufacturing, filling, andpackaging equipment in aseptic processes; disinfecting pharmaceuticaland cosmetic surfaces; poultry house disinfection; farm premisedisinfection; antimicrobial treatment of water filters, reverse osmosis(RO) and ultra-filtration (UF) membrane systems; boosters for alkalinedetergents to clean food processing equipment; boosters for aciddetergents to clean food processing equipment; sanitizing of hatchingeggs, coops, trucks, crates (poultry); food storage facilities;anti-spoilage air circulation systems; refrigeration and coolerequipment; beverage chillers and warmers, blanchers, cutting boards,third sink areas, and meat chillers or scalding devices; and the like.

In some aspects, the peracid compositions of the present invention areuseful in the cleaning or sanitizing of containers, processingfacilities, or equipment in the food service or food processingindustries. The compounds and compositions have particular value for useon food packaging materials and equipment, and especially for cold orhot aseptic packaging. Examples of process facilities in which thecompound of the invention can be employed include a milk line dairy, acontinuous brewing system, food processing lines such as pumpable foodsystems and beverage lines, etc. Food service wares can be disinfectedwith the compound of the invention. For example, the compounds can alsobe used on or in ware wash machines, low temperature ware wash machines,dishware, bottle washers, bottle chillers, warmers, third sink washers,cutting areas (e.g., water knives, slicers, cutters and saws) and eggwashers. Particular treatable surfaces include packaging such ascartons, bottles, films and resins; dish ware such as glasses, plates,utensils, pots and pans; ware wash and low temperature ware washmachines; exposed food preparation area surfaces such as sinks,counters, tables, floors and walls; processing equipment such as tanks,vats, lines, pumps and hoses (e.g., dairy processing equipment forprocessing milk, cheese, ice cream and other dairy products); andtransportation vehicles. Containers include glass bottles, PVC orpolyolefin film sacks, cans, polyester, PEN or PET bottles of variousvolumes (100 ml to 2 liter, etc.), one gallon milk containers, paperboard juice or milk containers, etc.

In a further embodiment, the peracid compositions can be employed in avariety of health care, laundry care and/or vehicle care environments.Still further, embodiments for use of the peracid compositions includecooling tower disinfection, biofilm reduction and the treatment of wastewater where both its antimicrobial function and its oxidant propertiescan be utilized.

The present peracid compositions can be employed for reducing thepopulation of pathogenic microorganisms, such as pathogens of humans,animals, and the like. The peracid compositions have activity against avariety of pathogens, including Gram positive (for example, Listeriamonocytogenes or Staphylococcus aureus) and Gram negative (for example,Escherichia coli or Pseudomonas aeruginosa) bacteria, yeast, molds,bacterial spores, viruses, etc. fungi, molds, bacteria, spores (e.g.endospores), and viruses. Such pathogens can cause a varieties ofdiseases and disorders.

As a result of the activity of the peracid compositions of theinvention, they can be used as or included in products such assterilants, sanitizers, disinfectants, preservatives, deodorizers,antiseptics, fungicides, germicides, sporicides, virucides, detergents,bleaches, hard surface cleaners, and pre- or post-surgical scrubs.

According to an embodiment of the invention, the peracid compositionsare utilized to kill one or more of the food-borne pathogenic bacteriaassociated with a food product, including, but not limited to,Salmonella, Campylobacter, Listeria, Escherichia coli, yeast, and mold.According to further embodiments, the peracid compositions of thepresent invention are utilized to kill one or more of the pathogenicbacteria associated with a health care surfaces and environmentsincluding, but not limited to, Salmonella, Staphylococcus, includingmethicillin resistant Staphylococcus aureus, Salmonella, Pseudomonas,Escherichia, mycobacteria, yeast, and mold. In still further embodimentsof the present invention, the peracid compositions can kill a widevariety of microorganisms on a food processing surface, on the surfaceof a food product, in water used for washing or processing of foodproduct, on a health care surface, or in a health care environment.

A concentrate or use concentration of the peracid compositions of thepresent invention can be applied to or brought into contact with anobject or surface by any conventional method or apparatus for applyingan antimicrobial or cleaning composition to an object or surface. Forexample, the object can be wiped with, sprayed with, and/or immersed inthe peracid composition, or a use composition made from the peracidcomposition. Contacting can be manual or by machine which may employ aliquid, gel, aerosol, gas, wax, solid, or powdered peracid compositionsaccording to the invention, or solutions containing these compositions.

According to an embodiment of the invention, upon application of theperacid compositions the object or surface may be moved with mechanicalaction, preferably agitated, rubbed, brushed, etc. Agitation can be byphysical scrubbing, through the action of the spray solution underpressure, through sonication, or by other methods. Agitation increasesthe efficacy of the spray solution in killing micro-organisms, perhapsdue to better exposure of the solution into the crevasses or smallcolonies containing the micro-organisms. According to furtherembodiments of the invention a use solution of the peracid compositioncan also be used at a temperature of about 10 to 70° C., preferablyabout 20 to 60° C. to increase efficacy.

A sprayed peracid composition can be left on a treated object or surfacefor a sufficient amount of time to suitably reduce the population ofmicroorganisms, and then rinsed, drained and/or evaporated off thetreated object or surface. The present methods require a certain minimalcontact time of the peracid composition for occurrence of significantantimicrobial effect. The contact time can vary with concentration ofthe use composition, method of applying the use composition, temperatureof the use composition, amount of soil on the treated object or surface,number of microorganisms on the treated object or surface, type ofantimicrobial agent, or the like. Preferably the exposure time is atleast about 5 to about 15 seconds.

Immersing an object or surface in a liquid peracid composition can beaccomplished by any of a variety of methods known to those of skill inthe art. For example, the object can be placed into a tank or bathcontaining the peracid composition. Alternatively, the object can betransported or processed in a flume of the peracid composition. Thewashing solution is preferably agitated to increase the efficacy of thesolution and the speed at which the solution reduces micro-organismsaccompanying the object. Agitation can be obtained by conventionalmethods, including ultrasonics, aeration by bubbling air through thesolution, by mechanical methods, such as strainers, paddles, brushes,pump driven liquid jets, or by combinations of these methods. Thewashing solution can be heated to increase the efficacy of the solutionin killing micro-organisms. After the object has been immersed for atime sufficient for the desired antimicrobial effect, the object can beremoved from the bath or flume and the peracid composition can berinsed, drained, or evaporated off the object.

In a further alternative embodiment of the present invention, an objector surface can be treated with a foaming version of the peracidcomposition. According to an embodiment of the invention, a foam can beprepared by mixing foaming surfactants with the washing solution at timeof use. The foaming surfactants can be nonionic, anionic or cationic innature. Examples of useful surfactant types include, but are not limitedto the following: alcohol ethoxylates, alcohol ethoxylate carboxylate,amine oxides, alkyl sulfates, alkyl ether sulfate, sulfonates,quaternary ammonium compounds, alkyl sarcosines, betaines and alkylamides. The foaming surfactant is typically mixed at time of use withthe washing solution. According to an embodiment, use solution levels ofthe foaming agents is from about 50 ppm to about 2.0 wt-%. Methods ofapplication can include the use of compressed air injected into themixture, then applied to the object or surface through a foamapplication device such as a tank foamer or an aspirated wall mountedroamer.

In another alternative embodiment of the present invention, an object orsurface can be treated with a thickened or gelled version of the peracidcomposition. In the thickened or gelled state the washing solutionremains in contact with the object or surface for longer periods oftime, thus increasing the antimicrobial efficacy. The thickened orgelled solution will also promote adherence of the peracid compositionto vertical surfaces. The composition or the washing solution can bethickened or gelled using existing technologies such as: xanthan gum,polymeric thickeners, cellulose thickeners, or the like. The thickenersor gel forming agents can be used either in the concentrated product ormixing with the washing solution, at time of use. Typical use levels ofthickeners or gel agents range from about 100 ppm to about 10 wt-%.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

A surface disinfectant with ethanol was formulated according to theperoxycarboxylic acid composition of the invention. The baseline formulafor the disinfectant (peroxycarboxylic acid composition) is set forth inTable 1.

TABLE 1 Item Description RM# %, w/w %, w/w 10 Biosoft S101 (LAS) 1750751-80% 34.190% 20 Propylene glycol 164079 1-50%  7.350% 30 Sulfuric acid,98% ACS grade 1-50%  3.000% 40 Sulfonated Oleic acid, European 1-50%13.140% 50% OPA 50 Hydrogen peroxide, 50% 240069 1-80% 42.180% 60Dipicolinic acid Aldrich 1-10%  0.140% 100.00%  100.00%

Varying amounts of ethanol were added to the baseline formulation as setforth below in Table 2. The various ethanol samples (EthOH-1 throughEtOH-5) varied in the strength of the odor from the ethanol, withincreasingly aggressive odor as the ethanol concentrations increased.EtOH-1 exhibited a subtle smell with increasingly proportional odoroutcomes as the percent ethanol increased to the EtOH-5 formulationwhich exhibited a sweet, cocktail smell.

TABLE 2 Ethanol SDA Baseline Formula (of Total, % Sample 40B, % (w/w)above) % (w/w) (w/w) EtOH-1 1.00 99.00 100.00 EtOH-2 2.00 98.00 100.00EtOH-3 3.00 97.00 100.00 EtOH-4 4.00 96.00 100.00 EtOH-5 5.00 95.00100.00

Table 3 shows the percentage peroxysulfonated oleic acid (PSOA)percentage hydrogen peroxide, and percentage available oxygen in eachformulation after two weeks of the varying peroxycarboxylic acidcompositions stored at about 40° C. for one week and then stored at roomtemperature for one week. Without the addition of ethanol to theperoxycarboxylic acid composition the composition identified in Table 1exhibited significant malodor within approximately two weeks (indicatingthe degradation of the peroxycarboxylic acid into the short chaincarboxylic acids responsible for the malodors. The EtOH-1, EtOH-2,EtOH-3, EtOH-4 and EtOH-5 formulations did not exhibit the malodors area result of the formulation including the ethanol (with proportionalincreases in the pleasant, fruity odor attributed to the formation ofethyl esters in the compositions).

TABLE 3 Time 2 wks (40 C. 1 wk + RT 1 wk) Sample % EtOH % PSOA412 % H₂O₂% av. O₂ EtOH-0 0.00 6.51 14.70 7.17 EtOH-1 1.00 5.90 16.43 7.96 EtOH-22.00 5.21 16.29 7.87 EtOH-4 4.00 4.47 17.09 8.22 EtOH-5 5.00 4.18 16.948.13

Table 4 shows the percentage peroxysulfonated oleic acid (PSOA)percentage hydrogen peroxide, and percentage available oxygen in eachformulation after one year of the varying peroxycarboxylic acidcompositions stored at room temperature. The formulation containing noethanol exhibited a significant malodor. Formulations EtOH-1 and EtOH-2exhibited a very subtle, pleasant odor. Formulations EtOH-4 and EtOH-5exhibited a very sweet, fruity odor. Notably, all EtOH-1 through EtOH-5formulation samples maintained their pleasant ester odors for at leastone year.

The percentage available oxygen in Table 4 is decreased in comparison tothe percentage available oxygen in Table 3, demonstrating the increasein degradation of the peroxycarboxylic acids of the composition.However, only formulation EtOH-0 demonstrated a malodor.

TABLE 4 Time ~1 year RT Sample % EtOH % PSOA412 % H₂O₂ % av. O₂ EtOH-00.00 9.15 13.80 6.85 EtOH-1 1.00 9.00 12.81 6.38 EtOH-2 2.00 8.12 11.215.59 EtOH-4 4.00 7.33 11.40 5.65 EtOH-5 5.00 7.38 11.51 5.70

Both Tables 3 and 4 show an expected slight decrease in percentagesulfonated perolic acid as a result of replacing peroxycarboxylic acidcontent with the ethanol. However, no significant degradation of theperoxycarboxylic acid content after up to a year of storage at roomtemperature demonstrates the unexpected increase in the composition'sshelf life. The slight loss in the peracid portion was significantlyless than expected (significant competition between formation of thepleasant-smelling esters and the peracid formulation was expected as aresult of the peracid formation being essentially identical to esterformation).

Example 2

A sample of the EtOH-0 formulation of Example 1 (malodor developedwithin about two weeks) was submitted for analysis by a vapor phase gaschromatography (GC) method. Using the GC technique, several sources ofthe malodor were identified, including, for example, butyric acid. Themalodor sources were all shorter chain carboxylic acids. As the longerchain peracids do not exhibit malodors (due to molecular weight andvapor pressure of the molecules), the GC technique confirms that thevarious decomposition products are responsible for these malodors.

Analysis of the formulations embodied in EtOH-1, EtOH-2, EtOH-3, EtOH-4and EtOH-5 show the formation of multiple esters responsible for thepleasant odors. Two principal ethyl esters formed include ethyl acetateand ethyl caprylate (also referred to as ethyl octanoate). The esterspossess very pleasant odors and are generally benign and approved foruse in food additives, etc.

Ethyl acetate is the esterification product of ethanol and acetic acid.It is a colorless liquid with a characteristic sweet fruity smell. It iscommonly used in the decaffeination process of coffee and tea because ofits solvent properties. It is allowed by the FDA as a secondary directfood additive (per 21 CFR173.228) and is also listed as an EPA inertingredient.

Ethyl octanoate is the esterification product of octanoic (caprylicacid). It is a colorless liquid used as a flavoring agent permitted fordirect addition to foods for human consumption with characteristic odorsincluding but not limited to fruity, floral, apricot, wine, brandy,pineapple, banana, apple, and tropical fruit. It is commonly used indairy products and alcoholic beverages (per 21 CFR 172.515 syntheticflavoring substances and adjuvants).

Example 3

The following alcohols were formulated according to the compositions ofthe invention for an odor assessment. Table 5 sets forth the samples andthe resulting odor assessment.

TABLE 5 Stock Alcohol Concentrate Portion Portion Odor Sample AlcoholType (%, w/w) (%, w/w) assessment A1 Ethanol 1 99 Pleasant, sweetpineapple-like A2 Ethanol 5 95 Strong fruity pineapple-like B11-Propanol 1 99 Weak, pleasant B2 1-Propanol 5 95 Weak, pleasant C12-Propanol 1 99 Weak, pleasant C2 2-Propanol 5 95 Weak, pleasant D1Benzyl alcohol 1 99 Weak, pleasant D2 Benzyl alcohol 5 95 Weak, pleasantE1 1-Nonanol 1 99 Weak, pleasant E2 1-Nonanol 5 95 Weak, pleasant

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims.

What is claimed is:
 1. A reduced odor peroxycarboxylic acid compositioncomprising: from about 0.01 wt-% to 50 wt-% of at least oneperoxycarboxylic acid; and from about 0.1 wt-% to 20 wt-% of an alcohol,wherein the alcohol is effective for forming alkyl esters under the sameconditions for peroxycarboxylic acid formation to reduce the malodors ofthe peroxycarboxylic acid compositions associated with short tomid-chain length carboxylic acids contaminants and/or those formed dueto degradation of a peroxycarboxylic acid composition.
 2. Thecomposition of claim 1, wherein the alcohol is selected from the groupconsisting of methanol, ethanol, propanol, butanol, nonanol, benzylalcohol and combinations of the same.
 3. The composition of claim 1,wherein at least one peroxycarboxylic acid is an alkyl peroxycarboxylicacid, a C₁-C₂₀ alkyl peroxycarboxylic acid and/or asulfoperoxycarboxylic acid.
 4. The composition of claim 1, wherein aready to use composition comprises from about 0.01 wt % to 10 wt-%peroxycarboxylic acid and from about 0.1 wt-% to 10 wt-% alcohol.
 5. Thecomposition of claim 1, further comprising an oxidizing agent comprisinghydrogen peroxide and/or at least one carboxylic acid.
 6. Thecomposition of claim 1, wherein the composition is stable for at least 1year at room temperature without the development of malodors andprovides at least substantially similar reduction in microorganisms as aperoxycarboxylic acid composition that does not comprise alkyl esters.7. The composition of claim 1, further comprising a hydrotropesurfactant selected from the group consisting of an anionic surfactant,alkyl sulfate, an alkyl or alkane sulfonate, a linear alkyl benzene ornaphthalene sulfonate, aryl sulfonates, a secondary alkane sulfonate, analkyl ether sulfate or sulfonate, an alkyl phosphate or phosphonate, adialkyl sulfosuccinic acid ester, a sugar ester, a C₈₋₁₀ alkyl glucosideand combinations thereof.
 8. The composition of claim 7, wherein thesurfactant is an antimicrobial anionic surfactant (e.g. dodecyl benzenesulfonic acid).
 9. The composition of claim 1, wherein the alcoholresults in a pleasant odor masking and/or derivatizing the compoundsresponsible for the malodors associated with a peroxycarboxylic acidcomposition.
 10. A method for generating reduced odor antimicrobialperoxycarboxylic acid composition comprising: providing a short chainalcohol to a peroxycarboxylic acid-generating composition, wherein thealcohol is provided before or during formation of peroxycarboxylic acidsto generate alkyl esters that are capable of removing and/or maskingshort to mid-chain carboxylic acids associated with malodors; andgenerating a peroxycarboxylic acid composition that is stable for atleast 1 year at room temperature without the development of malodors andcomprises from about 0.01 wt-% to 50 wt-% of at least oneperoxycarboxylic acid selected from the group consisting of an alkylperoxycarboxylic acid, a sulfoperoxycarboxylic acid and combinations ofthe same; and about 0.1 wt-% to 20 wt-% of an alcohol selected from thegroup consisting of methanol, ethanol, propanol, butanol, nonanol,benzyl alcohol and combinations of the same.
 11. The method of claim 10,wherein the alcohol is ethanol and wherein the peroxycarboxylic acid isperoxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleicacid.
 12. The method of claim 10, wherein the alcohol generates ethylester analogs of the peroxycarboxylic acids.
 13. The method of claim 10,wherein less than about 5 wt-% loss of peroxycarboxylic acid occurs dueto the formation of the esters.
 14. The method of claim 10, wherein theperoxycarboxylic acid composition further comprises at least onecarboxylic acid and an oxidizing agent comprising hydrogen peroxide. 15.The method of claim 10, wherein the peroxycarboxylic acid compositionfurther comprises a hydrotrope surfactant selected from the groupconsisting of an anionic surfactant, alkyl sulfate, an alkyl or alkanesulfonate, a linear alkyl benzene or naphthalene sulfonate, a secondaryalkane sulfonate, aryl sulfonates, an alkyl ether sulfate or sulfonate,an alkyl phosphate or phosphonate, a dialkyl sulfosuccinic acid ester, asugar ester, a C₈₋₁₀ alkyl glucoside and combinations thereof.
 16. Themethod of claim 10, wherein the generating of the peroxycarboxylic acidcomposition further comprises dehydrating the system and/or minimizingwater to favor esterification.
 17. A method of reducing population ofmicroorganism on an object, comprising: contacting an object with areduced-odor peroxycarboxylic acid comprising at least oneperoxycarboxylic acid and an alcohol, wherein the alcohol is effectivefor forming alkyl esters under the same conditions for peroxycarboxylicacid formation to reduce the odor of the peroxycarboxylic acid, andwherein the composition comprises from about 0.01 wt-% to 50 wt-%peroxycarboxylic acid and from about 0.1 wt-% to 20 wt-% alcohol. 18.The method of claim 17, wherein the object comprises a food processingor manufacturing surface, food tissue, food packaging, a health caresurface, medical or surgical devices, textiles, a body or stream ofwater, a body or stream of gas, a hospitality sector surface, anindustrial sector surface, an agricultural surface, a veterinarysurface, architectural surfaces, dishware, hard surface packaging, or acombination thereof.
 19. The method of claim 17, wherein theperoxycarboxylic acid composition provides at least substantiallysimilar reduction in microorganisms as a peroxycarboxylic acidcomposition that does not comprise the alkyl esters to remove and/ormask short chain malodors.
 20. The method of claim 17, wherein theperoxycarboxylic acid composition is present in an amount effective forreducing a population of a microorganism selected from the groupconsisting of spores, bacteria, mold, yeast, viruses and mixturesthereof, and wherein the microorganism is selected from the groupconsisting of B. cereus, B. subtilus, B. atrophaeus, C. difficile, C.sporogenes, Staph. aureus, methicillin-resistant Staph. aureus,Pseudomonas aeruginosa, E. coli and mixtures thereof.
 21. The method ofclaim 17, wherein the alcohol is selected from the group consisting ofmethanol, ethanol, propanol, butanol, nonanol, benzyl alcohol andcombinations of the same, and wherein the peroxycarboxylic acid isselected from the group consisting of an alkyl peroxycarboxylic acid, asulfoperoxycarboxylic acid and combinations of the same.